Toward accurate spin-state energetics of transition metal complexes

Radoń, Mariusz

doi:10.1016/bs.adioch.2018.10.001

Cited by 15 publications

(17 citation statements)

References 115 publications

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“…It is noteworthy that DFT-derived free energies must be considered cautiously, especially when redox-active transition metals are involved, as predicted ground-spin states and activation energies may strongly depend on the choice of a functional . Regarding reactions 1 – 8 , the correct ground-spin state is predicted in all cases with the exception of system 2 , where the HAA barrier is also underestimated.…”

Section: Resultsmentioning

confidence: 99%

Understanding and Predicting Post H-Atom Abstraction Selectivity through Reactive Mode Composition Factor Analysis

Maldonado-Domínguez

Srnec

2020

J. Am. Chem. Soc.

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The selective functionalization of C–H bonds is one of the Grails of synthetic chemistry. In this work, we demonstrate that the selectivity toward fast hydroxylation or radical diffusion (known as the OH-rebound and dissociation mechanisms) following H-atom abstraction (HAA) from a substrate C–H bond by high-valent iron-oxo oxidants is already encoded in the HAA step when the post-HAA barriers are much lower than the preceding one. By applying the reactive mode composition factor (RMCF) analysis, which quantifies the kinetic energy distribution (KED) at the reactive mode (RM) of transition states, we show that reactions following the OH-rebound coordinate concentrate the RM kinetic energy on the motion of the reacting oxygen atom and the nascent substrate radical, whereas reactions following the dissociation channel localize most of their kinetic energy in H-atom motion. These motion signatures serve to predict the post-HAA selectivity, and since KED is affected by the free energy of reaction and asynchronicity (factor η) of HAA, we show that bimolecular HAA reactions in solution that are electron transfer-driven and highly exergonic have the lowest fraction of KED on the transferred H-atom and the highest chance to follow rebound hydroxylation. Finally, the RMCF analysis predicts that the H/D primary kinetic isotope effect can serve as a probe for these mechanisms, as confirmed in virtually all reported examples in the literature.

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Section: Resultsmentioning

confidence: 99%

Understanding and Predicting Post H-Atom Abstraction Selectivity through Reactive Mode Composition Factor Analysis

Maldonado-Domínguez

Srnec

2020

J. Am. Chem. Soc.

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“…It is also true for n:3 at the UB3LYP/6-311++G(d,p) level, however, at the UB3LYP/cc-PVDZ level the quartet state is more stable than the doublet. For energies of isomeric structures B3LYP functional bias in favor of one type of spin states of isomeric structures [37][38][39][40]. In the case of some aluminized explosives lower spin state is favored (UB3LYP/6-311++G(d,p)) [41][42][43].…”

Section: Resultsmentioning

confidence: 99%

A DFT Treatment of Some Aluminized 1,3,3-Trinitroazetidine (TNAZ) Systems - A Deeper Look

Türker

2020

EJCS

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1,3,3-Trinitroazetedine (TNAZ) is a powerful but insensitive energetic compound having C-NO2 and N-NO2 groups attached to a four-membered backbone. Aluminum powders are often added to explosives in order to have enhanced blast effect, etc. In the present study, aluminized TNAZ system is modeled for 1-3 Al atom(s) per TNAZ molecule within the restriction of density functional theory at the levels of UB3LYP/6-311++G(d,p) and UB3LYP/cc-PVDZ. Certain structural, physical and quantum chemical properties are obtained and discussed. The considered properties are found to be highly dependent on the multiplicity (thus the number of Al atoms present) of the composite systems considered. Also, calculated IR and UV-VIS spectra of the composites have been presented.

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“…However, certain energetic properties of TMI sites with potential relevance in catalysis, such as metal–ligand bond energies and spin-state splittings, are known to be computationally much more problematic [ 105 , 106 , 107 , 108 ]. For such challenging electronic properties, not only are the computed results strongly dependent on the choice of functional (with discrepancies of ~50 kJ mol −1 not being rare), but the optimal choice of functional is also system dependent (in particular, it is dependent on the TMI oxidation state and its coordination environment, including ligand field strength or binding mode), so that finding functionals that perform universally well for different systems is currently problematic [ 109 , 110 , 111 , 112 ].…”

Section: Transition Metal Ions: the Challenge For Electronic Strucmentioning

confidence: 99%

Zeolites at the Molecular Level: What Can Be Learned from Molecular Modeling

et al. 2021

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Toward accurate spin-state energetics of transition metal complexes

Cited by 15 publications

References 115 publications

Understanding and Predicting Post H-Atom Abstraction Selectivity through Reactive Mode Composition Factor Analysis

Understanding and Predicting Post H-Atom Abstraction Selectivity through Reactive Mode Composition Factor Analysis

A DFT Treatment of Some Aluminized 1,3,3-Trinitroazetidine (TNAZ) Systems - A Deeper Look

Zeolites at the Molecular Level: What Can Be Learned from Molecular Modeling

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